Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
  • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/307—General preparatory processes using carbonates and phenols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/02—Ortho- or ortho- and peri-condensed systems
  • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
  • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
  • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
  • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
  • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

• the present invention relates to compounds with a fluorene backbone, that are suitable as monomers for forming thermoplastic resins that are to form optical members such as optical lenses or optical films, and that are suitable as starting materials for thermoplastic resins with a high refractive index, low birefringence and excellent balance between heat resistance and moldability, as well as to a method for producing the compounds.
• thermoplastic resin materials such as polycarbonates, polyesters and polyester carbonates wherein the starting materials are alcohols with fluorene backbones, among which 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) is typical, for use as optical members including optical lenses and optical sheets, because they have excellent optical characteristics, heat resistance and moldability.
• BPEF 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene
• PTL 1 discloses a polycarbonate resin wherein the starting material is an alcohol with a BPEF backbone.
• the refractive index of the polycarbonate resin using such an alcohol is given as 1.64, rapid technological innovation in recent years has led to demand for even better properties.
• PTL 2 describes a thermoplastic resin developed using 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene (BOPBPEF) as the starting material, but the resin described in this patent document is also in need of improvement in the refractive index.
• BOPBPEF 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene
• PTL 3 also describes a high-refractive-index resin using 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene (BNEF) as the starting material, but since the birefringence is also high with the higher refractive index, it is associated with significant problems when applied as a transparent material for an optical lens.
• BNEF 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene
• BPEF 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene
• NPL 1 phenoxyethanol
• BNEF 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene
• PTL 4 sulfuric acid and a thiol are used as catalysts for dehydrating condensation of fluorenone and 2-naphthoxyethanol
• BOPBPEF 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene
• BNEF BNEF
• sulfuric acid and a thiol are used as catalysts for dehydrating condensation of fluorenone and 2-(2-biphenylyloxy)ethanol (PTL 5)
• PTL 5 2-(2-biphenylyloxy)ethanol
• all of these methods use large amounts of sulfuric acid, it is necessary to carry out complex purification procedures after reaction, such as neutralization and purification, and this generates a large amount of neutralizing waste water.
• inclusion of sulfur components from the catalyst into the product leads to problems such as product coloration, lower stability and lower purity.
• To obtain a high-purity product such as a resin material for optical use it is also necessary to repeat the purification procedure for removal of the sulfur components, and therefore the method cannot be considered to be industrially advantageous.
• step 2 or step (a) The method for producing molecularly designed compounds of the following formula (1) according to the invention consists of the two steps outlined below, but even if the alcohol is synthesized using the following formula (6) or (3) and the following formula (7) by the methods described in the aforementioned patent documents, the reaction of step 2 or step (a) is industrially disadvantageous because the reaction either fails to proceed at all, or the reaction rate is slow even if it does proceed.
• step 1 or step (b) when a large amount of catalyst is used in step 1 or step (b) and activated carbon treatment or very similar metal removal treatment is not carried out, then black particles deriving from the palladium catalyst used in the reaction of step 1 or step (b) mixes with the white compound with a fluorene backbone represented by the following formula (1), thus impairing the color tone of the alcohol compound.
• the present invention which has been devised as a result of research on solving the aforementioned problems of the prior art, provides compounds with a fluorene backbone that have consistent quality and are superior as polymer starting materials, and a method for producing them. Specifically, the invention relates to the following compounds with a fluorene backbone and method for producing them.
• the fluorene compounds of the invention have a low content of specified metals, such as palladium, and a low content of specified compounds, and therefore thermoplastic resins obtained using such fluorene compounds as starting materials have excellent optical characteristics as well as excellent physical properties (heat resistance, color tone and moldability). According to the invention it is also possible to efficiently produce compounds with a fluorene backbone having such excellent properties.
• mixture of compounds means a composition including or consisting of, in addition to these compounds, impurities that are by-products of production of the compounds and impurities deriving from substances used in the production.
• the mixture of the invention is a mixture of compounds with a fluorene backbone represented by the following formula (1), i.e. compounds with a substitution or addition of two aromatic hydrocarbons having at least one hydroxy group, at position 9 of a fluorene.
• the rings Z represent the same or different aromatic hydrocarbon rings
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to 12 carbon atoms optionally containing an aromatic group
• Ar 1 and Ar 2 represent optionally substituted aromatic groups of 6 to 10 carbon atoms
• L 1 and L 2 represent alkylene groups
• j and k each independently represent an integer of 0 or greater
• m and n each independently represent an integer of 0 to 5.
• the aromatic groups represented by rings Z in formula (1) may be benzene rings or fused polycyclic aromatic hydrocarbons having at least a benzene ring backbone, with preferred examples being fused bi- to tetracyclic hydrocarbon rings such as fused bicyclic hydrocarbons and fused tricyclic hydrocarbons.
• a fused bicyclic hydrocarbon ring is preferably an indene ring or naphthalene ring of 8 to 20 carbon atoms (hereunder also indicated as “C 8-20 "), and more preferably a C 10-16 fused bicyclic hydrocarbon ring.
• a fused tricyclic hydrocarbon ring is preferably an anthracene ring or phenanthrene ring.
• Benzene ring and naphthalene ring are preferred for the rings Z, with benzene ring being more preferred.
• preferred aromatic hydrocarbon rings represented by the rings Z in formula (1) are 1,4-phenylene group, 1,4-naphthalenediyl group and 2,6-naphthalenediyl group, with 1,4-phenylene group being more preferred.
• the two rings Z substituted at position 9 of the fluorene ring may be identical or different, and more preferably they are identical rings.
• the substituents on the rings Z substituting at position 9 of the fluorene backbone are not particularly restricted.
• the groups corresponding to the rings Z substituting at position 9 of the fluorene ring may be 1-naphthyl or 2-naphthyl groups.
• R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group optionally containing an aromatic group of 1 to 12 carbon atoms, with a hydrogen atom, a methyl group or a phenyl group being preferred.
• hydrocarbon groups represented by R 1 and R 2 in formula (1) include alkyl groups, cycloalkyl groups, aryl groups, naphthyl groups and aralkyl groups.
• alkyl groups include C 1-6 alkyl groups, C 1-4 alkyl groups or C 1-3 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups, with C 1-3 alkyl groups being more preferred, and methyl and ethyl groups being even more preferred.
• cycloalkyl groups include C 5-8 cycloalkyl groups and C 5-6 cycloalkyl groups such as cyclopentyl and cyclohexyl groups, with C 5-6 cycloalkyl groups being preferred.
• aryl groups include phenyl and alkylphenyl groups (such as mono- or dimethylphenyl, tolyl, 2-methylphenyl and xylyl groups), with phenyl group being preferred.
• aralkyl groups include C 6-10 aryl-C 1-4 alkyl groups such as benzyl and phenethyl groups.
• Preferred halogen atoms are fluorine, chlorine and bromine.
• substituent numbers j and k for substituents R 1 and R 2 are not particularly restricted and may be selected as appropriate for the number of fused rings of the fused hydrocarbon, but they are preferably each independently integers of 0 or greater, and more preferably 1 or greater. They are also preferably integers of no greater than 6 and more preferably integers of no greater than 4.
• the number of substituents j and k in the rings Z may be the same or different, but in most cases they will be the same.
• L 1 and L 2 each independently represent a divalent linking group, which is preferably an alkylene group of 1 to 12 carbon atoms, and more preferably an ethylene group.
• L 1 and L 2 will usually be identical alkylene groups on the same ring Z.
• L 1 and L 2 may also be the same or different on different rings Z, but normally they will be the same.
• the numbers (numbers of moles of addition) of the oxyalkylene groups (OL 1 ) and (OL 2 ) m and n may each be selected within a range of 0 to 5, with the lower limit being preferably 0 or greater and the upper limit being preferably 4 or lower, more preferably 3 or lower and even more preferably 2 or lower. They are preferably 0 or 1, and most preferably 1.
• the values of m and n may be integers or average values, and they may be the same or different on different rings Z.
• Ar 1 and Ar 2 each independently represent an aromatic group of 6 to 10 carbon atoms, and are preferably phenyl groups or naphthyl groups.
• the groups Ar 1 and Ar 2 may be different from each other or identical, but they will usually be identical.
• the bonding positions of Ar 1 and Ar 2 are preferably position 1 and position 8, position 2 and position 7, position 3 and position 6 or position 4 and position 5, more preferably position 2 and position 7, position 3 and position 6 or position 4 and position 5, and even more preferably position 2 and position 7, of the fluorene backbone.
• Preferred diphenylfluorene types include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-diphenylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxyphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-diphenylfluorene, 9,9-bis(4-hydroxy-3-phenylflu
• Preferred dinaphthylfluorene types include 9,9-bis(4-(2-hydroxyethoxy)phenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-1-naphthyl)-1,8-dinaphthylfluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)-1,8-dinaphthylfluorene, 9,9-bis(4-hydroxyphenyl)-1,8-dinaphthylfluorene, 9,9-bis(4-hydroxy-3-methylphenyl)-1,8-dina
• a mixture of compounds with a fluorene backbone according to the invention has a palladium element content satisfying the following inequality (2). 0 ⁇ Pd ⁇ 50 ppm
• the lower limit for the palladium element content may be 0.01 ppm or greater, 0.05 ppm or greater or 0.10 ppm or greater.
• Exceeding the upper limit of this range is not preferred because it can potentially have an adverse effect on productivity (or reactivity) for a resin using the starting alcohol represented by formula (1), and the physical properties (heat resistance, moldability and dimensional stability) of the produced resin.
• the method for producing compounds with a fluorene backbone represented by formula (1) or their mixture according to the invention is preferably [I] a production method including at least the following step 1 and step 2, or [II] a production method including at least the following step (a) and step (b).
• Production method [I] is largely divided into two steps, allowing production by a first step 1 in which a fluorenone represented by the following formula (3) is reacted with a boronic acid represented by the following formula (4) or (5), and a second step 2 in which the reaction product (6) produced by the first step is reacted with an alcohol compound represented by the following formula (7).
• the compound with a fluorene backbone or its mixture according to the invention can be produced conveniently and efficiently because reactivity of the boronic acid represented by the following formula (4) or (5) is high and secondary reactions do not occur, while the alcohol represented by the following formula (7) also acts as the reaction solvent and can be easily removed by distillation under reduced pressure.
• the compounds represented by formula (3) are fluorenone compounds corresponding to the fluorene backbone in formula (1), where X 1 is a substituent at position 1, position 2, position 3 or position 4, X 2 is a substituent at position 5, position 6, position 7 or position 8, and X 1 and X 2 are both halogen atoms.
• Preferred ones are 1,8-difluorofluorenone, 2,7-difluorofluorenone, 3,6-difluorofluorenone, 4,5-difluorofluorenone, 1,8-dichlorofluorenone, 2,7-dichlorofluorenone, 3,6-dichlorofluorenone, 4,5-dichlorofluorenone, 1,8-diiodofluorenone, 2,7-diiodofluorenone, 3,6-diiodofluorenone, 4,5-diiodofluorenone, 1,8-dibromofluorenone, 2,7-dibromofluorenone, 3,6-dibromofluorenone and 4,5-dibromofluorenone.
• 1,8-dibromofluorenone 1,8-dibromofluorenone, 2,7-dibromofluorenone, 3,6-dibromofluorenone and 4,5-dibromofluorenone, with 2,7-dibromofluorenone being especially preferred.
• the purity of the fluorenone represented by formula (3) is not particularly restricted, but usually it is preferred to be 95% or higher, and more preferably 99% or higher.
• the fluorenone that is used may be a commercial product or a synthesized product.
• An example of a method for producing dibromofluorenones is described in non-patent literature ( Journal of American Chemical Society, 2017, Vol. 139, 11073-11080 ), and specifically, it is a method of reacting 9-fluorenone and bromine in water.
• Ring Y in a compound represented by formula (4) or (5) corresponds to the groups Ar 1 and Ar 2 in formula (1), and its preferred instances are the same as for Ar 1 and Ar 2 .
• the preferred instances for group R 11 in formulas (4) and (5) are the same as the preferred ones for R 1 and R 2 , and the preferred instances for 1 are the same as the preferred ones for j and k.
• the purity of the boronic acid that is used is not particularly restricted, but usually it is preferred to be 95% or higher, and more preferably 99% or higher.
• the boronic acid that is used may be a commercial product or a synthesized product.
• An example of a method of producing boronic acids is described in patent literature (Japanese Unexamined Patent Publication No. 2002-47292 ), and specifically, it is a method of reacting a phenyl Grignard reagent with a boric acid ester dissolved in a non-ether-based aromatic solvent.
• Boronic acids to be used for the invention include alkylboronic acids, alkenylboronic acids, arylboronic acids and heteroarylboronic acids represented by formulas (4) and (5) and their anhydrides, with alkylboronic acids including butylboronic acid, cyclohexylboronic acid, cyclopentylboronic acid, 2-ethylboronic acid, 4-ethylboronic acid, hexylboronic acid, isobutylboronic acid, isopropylboronic acid, methylboronic acid, n-octylboronic acid, propylboronic acid, pentylboronic acid, 2-phenylethylboronic acid and their anhydrides, alkenylboronic acids including 1-cyclopentenylboronic acid, ferroceneboronic acid and 1,1'-ferrocenediboronic acid and their anhydrides, arylboronic acids including 2-anthraceneboronic acid, 9-anthraceneboronic acid
• Preferred for the invention are phenylboronic acid and 2-naphthaleneboronic acid, and their anhydrides.
• the usage ratio of the compound represented by formula (4) to be used as a starting material is about preferably 2 to 5 mol, more preferably 2.05 to 3.0 mol and even more preferably 2.00 to 2.5 mol, with respect to 1 mol of the compound represented by formula (3) (fluorenone halide compound). If the boronic acid is used at less than 2 mol, the yield of product represented by formula (6) may be lowered. If it is greater than 2.5 mol, the reaction rate and yield will be high, but production cost for the compound with a fluorene backbone may also increase.
• the usage ratio of the compound represented by formula (5) may be about preferably 1 to 5 mol, more preferably 0.8 to 3 mol and even more preferably 0.7 to 1 mol, with respect to 1 mol of the compound represented by formula (3) (fluorenone halide compound). If the boronic acid is used at less than 0.7 mol, the yield of product represented by formula (6) may be lowered. If it is greater than 1 mol, the reaction rate and the yield will be high, but production cost for the compound with a fluorene backbone may also increase.
• the reaction (dehalogenation reaction) between the compounds represented by formula (3) and formula (4) and/or (5) in step 1 may be carried out in a reaction solvent, in the presence of a base and a palladium-based catalyst.
• bases to be used in the reaction of step 1 include inorganic salts, among which are hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ) and cesium carbonate (Cs 2 CO 3 ), acetates such as sodium acetate and potassium acetate and phosphates such as sodium phosphate (Na 3 PO 4 ) and potassium phosphate (K 3 PO 4 ), triethylamines, pyridine, morpholine, quinoline, piperidine, anilines, and organic salts including ammonium salts such as tetra-n-butylammonium acetate. Carbonates are preferably used among these, with potassium carbonate and/or sodium carbonate being more preferred. Such bases may be used alone, or two or more may be used in combination.
• hydroxides such as sodium hydroxide and potassium hydroxide
• carbonates such as sodium carbonate (Na 2 CO 3 ), potassium carbonate (K
• the amount of such bases used in the reaction of step 1 is not particularly restricted, but is preferably added at 1 to 30 equivalents and more preferably 1 to 10 equivalents with respect to 1 mol of the boronic acid.
• the palladium-based catalyst to be used in the reaction of step 1 is preferably a palladium compound used in Suzuki coupling, examples of which include tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis[4-(N,N-dimethylamino)phenyl]di- tert -butylphosphinepalladium dichloride, bis(di-tert- butylprenyl)palladium dichloride and bis(di- tert -crotylphosphine)palladium dichloride.
• Preferred among these are tetrakis(triphenylphosphine)palladium and/or palladium acetate.
• Such catalysts may be used alone, or two or
• the amount of catalyst used in the reaction of step 1 is not particularly restricted, but it is preferably 0.5 to 10 millimole and more preferably 0.6 to 5 millimole, in terms of palladium metal atoms, with respect to 1 mol of the fluorenone compound represented by formula (3). If the amount of palladium catalyst used is less than 0.5 millimoles in terms of palladium metal atoms, it may be difficult for the reaction to proceed to completion.
• the amount of palladium catalyst used is greater than 10 millimole in terms of palladium metal atoms, the reaction will proceed to completion but it will be difficult to limit the palladium element content of the compound with a fluorene backbone to within the range of formula (2), not only potentially impairing the color tone of the thermoplastic resin produced using the alcohol starting material, but also increasing production cost for the compound with a fluorene backbone, in some cases.
• reaction solvents to be used in step 1 include aromatic hydrocarbon-based solvents such as toluene or xylene and alcohols such as methanol, ethanol, isopropyl alcohol and n-butanol, either alone or in combinations. Since an aromatic hydrocarbon-based solvent is a high boiling point solvent, the reaction temperature can be set higher, while using an alcohol is suitable for high affinity with water and satisfactory reactivity. Such solvents may be used alone, or two or more may be used in combination. An aprotic solvent such as N,N-dimethylformamide or N,N-dimethylacetamide or a halobenzene such as o-dichlorobenzene may also be used. Such solvents may be used alone, or two or more may be used in combination. According to the invention, a mixed solvent of toluene and ethanol, or toluene alone, may be used.
• aromatic hydrocarbon-based solvents such as toluene or xylene and alcohols
• alcohols such as
• the amount of reaction solvent (for the purpose of the invention, a mixed solvent of toluene and ethanol or toluene alone) that is used is not particularly restricted, but the amount of toluene is preferably 0.1 times by weight, more preferably 0.5 to 100 times by weight and even more preferably 1 to 50 times by weight, with respect to the fluorenone represented by formula (3). If the amount of toluene used is less than 0.1 times by weight, the product can potentially precipitate out and create difficulties for stirring. If the amount of toluene used is greater than 100 times by weight, the effect will not be commensurate with the increased amount of usage, while the volumetric efficiency may also be impaired, increasing production cost for the compound with a fluorene backbone.
• the amount of ethanol used is also not particularly restricted, but it is preferably 0.1 to 50 times by weight and more preferably 1 to 20 times by weight with respect to the fluorenone represented by formula (3). If the amount of ethanol used is less than 0.1 times by weight the reaction rate may be slowed, lowering the yield. If the amount of ethanol used is greater than 50 times by weight, the effect will not be commensurate with the increased amount of usage, as with toluene, while the volumetric efficiency may also be impaired, increasing production cost for the compound with a fluorene backbone.
• the reaction temperature will differ depending on the type of starting materials and solvent used, but it is preferably 50 to 150°C, more preferably 60 to 130°C and even more preferably 70 to 120°C.
• the reaction can be monitored by analysis means such as liquid chromatography.
• reaction mixture Upon completion of the reaction, the reaction mixture will generally contain unreacted fluorenone, unreacted boronic acid, base, catalyst and secondary reaction products, in addition to the product compound represented by formula (6). Therefore, separation and purification may be carried out by separation means using a common method such as filtration, concentration, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or highly similar metal removal treatment, or column chromatography, or a combination of these.
• purification may be carried out by removing the boronic acid by a common method (such as a method of adding an aqueous alkali solution to form a water-soluble complex), and removing the palladium compound by activated carbon treatment or highly similar metal removal treatment, and then adding a recrystallization solvent, cooling for recrystallization, and separating by filtration.
• a common method such as a method of adding an aqueous alkali solution to form a water-soluble complex
• the compound represented by formula (7) corresponds to a (poly)hydroxyl group-containing arene ring substituted at position 9 in a diarylfluorene derivative represented by formula (6).
• ring Z corresponds to ring Z in formula (1)
• R 12 corresponds to L 1 and L 2
• p corresponds to m and n
• R 13 corresponds to R 1 and R 2 and s corresponds to j and k
• the benzene rings and naphthalene rings mentioned above are examples.
• the alkylene group represented by R 12 is not particularly restricted, and may be an ethylene, propylene, trimethylene, tetramethylene or hexamethylene group, for example. It is preferably an alkylene group of 1 to 6 carbon atoms, and more preferably an alkylene group of 2 to 3 carbon atoms.
• the substitution position for R 12 is not particularly restricted.
• the number of substituents p is 0, 1 or greater, in which case they may be the same or different. It is preferably 0 to 15 and more preferably 0 to 5.
• the polyalkoxy group may be composed of identical alkoxy groups or composed of a combination of different alkoxy groups (for example, an ethoxy group and a propyleneoxy group), but it will usually be composed of identical alkoxy groups.
• R 13 represents a hydrogen atom, a halogen atom or a hydrocarbon group optionally containing an aromatic group of 1 to 12 carbon atoms, with a hydrogen atom, a methyl group or a phenyl group being preferred.
• hydrocarbon groups represented by R 13 include alkyl, cycloalkyl, aryl, naphthyl and aralkyl groups.
• alkyl groups include C 1-6 alkyl groups, C 1-4 alkyl groups or C 1-3 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl and t-butyl groups, with C 1-3 alkyl groups being more preferred, and methyl and ethyl groups being even more preferred.
• cycloalkyl groups include C 5-8 cycloalkyl groups and C 5-6 cycloalkyl groups such as cyclopentyl and cyclohexyl groups, with C 5-6 cycloalkyl groups being preferred.
• aryl groups include phenyl and alkylphenyl groups (such as mono- or dimethylphenyl, tolyl, 2-methylphenyl and xylyl groups), with phenyl group being preferred.
• aralkyl groups include C 6-10 aryl-C 1-4 alkyl groups such as benzyl and phenethyl groups. Preferred halogen atoms are fluorine, chlorine and bromine.
• R 13 substituents may be selected as appropriate depending on the number of fused rings of the fused hydrocarbon and is not particularly restricted, and it may be an integer of preferably 0 or greater and more preferably 1 or greater. It is also preferably an integer of no greater than 6 and more preferably an integer of no greater than 4.
• Examples where p is 2 or greater include the polyoxyalkylene phenyl ethers corresponding to these phenoxyalkyl alcohols. Preferred are phenoxy C 2-6 alkyl alcohols or C 1-4 alkylphenoxy C 2-6 alkyl alcohols, with phenoxyethanol being most preferred.
• the amount of compound represented by formula (7) used in the reaction of step 2 is not particularly restricted, but from the viewpoint of inhibiting secondary reactions and for economy, it is preferably 2 to 50 mol, more preferably 2.5 to 20 mol and even more preferably 3 to 10 mol, with respect to 1 mol of the fluorenone. These compounds may also be used as the reaction solvent.
• the compounds represented by formula (7) may be commercial products or synthesized products.
• the method for producing a compound represented by formula (7) may be, for example, a method in which the hydroxyl groups of phenols are reacted using ethylene oxide and ethylene carbonate, in the presence of an alkali catalyst.
• the purity of the compound represented by formula (7) used as a starting material is not particularly restricted, but usually it is preferred to be 95% or higher, and more preferably 99% or higher.
• step 2 will usually be carried out in the presence of an acid catalyst.
• acid catalysts include sulfuric acid, thiolic acid, montmorillonite and heteropolyacids, among which heteropolyacids are preferred because they have low formation of acid catalyst-derived impurities and can facilitate production of the compound with a fluorene backbone according to the invention.
• heteropolyacid used for heteropolyacids that may be suitably used for the invention generally includes those produced by fusion of two or more different inorganic oxo acids, with there being a variety of possible heteropolyacids obtained by combining a central oxo acid with different types of oxo acids fused around it.
• hetero elements A small number of elements that form central oxo acids are referred to as “hetero elements”, and elements forming oxo acids that fuse around it are referred to as "poly elements”.
• the poly elements may be of a single type or of multiple different types.
• hetero element for an oxo acid forming a heteropolyacid
• examples include copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium and platinum.
• Phosphorus (phosphoric acid) and silicon (silicic acid) are preferred.
• oxo acids forming a heteropolyacid there are also no particular restrictions on the poly elements of oxo acids forming a heteropolyacid, and examples include vanadium, molybdenum, tungsten, niobium and tantalum. They are preferably one or more selected from among vanadium, molybdenum and tungsten.
• the heteropolyacid anion used to form the heteropolyacid backbone may be one with any of various different compositions. Examples include XM 12 O 40 , XM 12 O 42 , XM 18 O 62 and XM 6 O 24 .
• a preferred composition for the heteropolyacid anion is XM 12 O 40 .
• X is the hetero element and M represents a poly element.
• Specific examples of heteropolyacids with these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid and phosphovanadomolybdic acid.
• the heteropolyacid may be a free heteropolyacid, or alternatively a heteropolyacid salt with some or all of the protons replaced with other cations may be used. Therefore, a "heteropolyacid" for the purpose of the invention includes such heteropolyacid salts. Examples of cations that may replace the protons include ammonium, alkali metals and alkaline earth metals.
• the heteropolyacid may be an anhydride or a substance containing water of crystallization, but an anhydride is preferred for more rapid reaction and less formation of by-products. With a substance containing water of crystallization, the same effect can be achieved as with an anhydride if dehydrating treatment is carried out beforehand by reduced pressure drying or azeotropic dehydration with a solvent.
• the heteropolyacid may be used in a form supported on a carrier such as active carbon, alumina, silica-alumina or diatomaceous earth.
• the heteropolyacids may be used alone, or two or more may be used in combination. If necessary, another catalyst other than a heteropolyacid may also be used in a range that does not interfere with the object of the invention.
• the amount of heteropolyacid used is not particularly restricted, but in order to obtain a sufficient reaction rate it is preferably at least 0.0001 times by weight, more preferably 0.001 to 30 times by weight and even more preferably 0.01 to 5 times by weight, with respect to the fluorenone.
• the method of carrying out the reaction of step 2 is not particularly restricted, but it can generally be carried out by charging the compounds represented by formula (6) and formula (7) together with a heteropolyacid into a reactor, and heating and stirring them in air or under an inert gas atmosphere of nitrogen or argon, in the presence or in the absence of an inert solvent such as toluene or xylene.
• an inert solvent such as toluene or xylene.
• the dehydration method is not particularly restricted and may be dehydration by addition of a dehydrating agent, dehydration by pressure reduction, or dehydration by azeotropic distillation with a solvent at ordinary pressure or under reduced pressure.
• the solvent for azeotropic dehydration is not particularly restricted, and it may be an aromatic hydrocarbon solvent such as toluene or xylene, an aromatic halide hydrocarbon solvent such as chlorobenzene or dichlorobenzene, an aliphatic hydrocarbon solvent such as pentane, hexane or heptane, a halogenated aliphatic hydrocarbon solvent such as dichloromethane or 1,2-dichloroethane, an aliphatic or cyclic ether solvent such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran or dioxane, an ester solvent such as ethyl acetate or butyl acetate, a nitrile solvent such as acetonitrile, propionitrile, butyronitrile or benzonitrile, or an amide solvent such as N,N-dimethylform
• an aromatic hydrocarbon solvent or aromatic halide hydrocarbon solvent more preferably toluene, xylene, chlorobenzene or dichlorobenzene, and even more preferably toluene.
• the amount used is not particularly restricted, but from the viewpoint of economy it is preferably at least 0.1 times by weight, more preferably 0.5 to 100 times by weight and even more preferably 1 to 20 times by weight, with respect to the fluorenone.
• the reaction temperature will differ depending on the type of starting materials and solvent used, but it is preferably 50 to 300°C, more preferably 80 to 250°C and even more preferably 120 to 180°C.
• the reaction can be monitored by analysis means such as liquid chromatography.
• the obtained reaction mixture may be used directly to precipitate the compound represented by formula (1), but usually the compound represented by formula (1) is precipitated at lower than 50°C after post-treatment such as rinsing, concentration, dilution and activated carbon treatment.
• the procedure for precipitating the compound represented by formula (1) from the reaction mixture that has been post-treated as necessary is carried out by raising the temperature of the reaction mixture, combined with a solvent if necessary, to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooling it to lower than 50°C.
• the reaction mixture When crystals of the compound represented by formula (1) precipitate from the reaction mixture at 50°C or higher, the reaction mixture may be mixed with a diluting solvent in an amount so that crystals do not precipitate out at 50°C or higher, and the temperature of the obtained mixture may then be raised to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooled to lower than 50°C.
• a diluting solvent in an amount so that crystals do not precipitate out at 50°C or higher
• the temperature of the obtained mixture may then be raised to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooled to lower than 50°C.
• the diluting solvent may be any of the examples mentioned above as solvents to be used for the reaction, or an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol or pentanol or a carbonate solvent such as dimethyl carbonate or diethyl carbonate, but it is preferably butanol or dimethyl carbonate, and most preferably butanol.
• an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol or pentanol
• a carbonate solvent such as dimethyl carbonate or diethyl carbonate, but it is preferably butanol or dimethyl carbonate, and most preferably butanol.
• the crystallization procedure may be carried out once or repeated several times.
• the acid catalyst in the reaction of step 2 is phosphotungstic acid
• using an alcohol such as butanol allows a compound represented by formula (1) satisfying formula (2) to be obtained in a convenient and efficient manner with only a single crystallization procedure.
• the precipitated crystals are recovered by filtration, for example.
• the crystals may be rinsed using the solvent used for the reaction, and they may also be dried.
• the purity of the purified compound represented by formula (1) that is obtained in this manner is preferably 95% or greater.
• the purity of a compound with a fluorene backbone obtained by the production method of the invention may be selected within a wide range of 60 to 100%, but it is preferably 70% or greater, more preferably 80% or greater and even more preferably 90% or greater.
• Production method [II] is largely divided into two steps, allowing production by a first step (a) in which a fluorenone represented by the following formula (3) is reacted with an alcohol compound represented by the following formula (7), and a second step (b) in which the reaction product (8) produced by the first step (a) is reacted with a boronic acid represented by the following formula (4) or (5).
• the compound with a fluorene backbone or its mixture according to the invention can be produced conveniently and efficiently because the alcohol represented by the following formula (7) also acts as the reaction solvent and can be easily removed by distillation under reduced pressure, while reactivity of the boronic acid represented by the following formula (4) or (5) is high and secondary reactions do not occur.
• the compound represented by formula (3) may be a compound represented by formula (3) as described above for Production method [I].
• the compound represented by formula (7) corresponds to a (poly)hydroxyl group-containing arene ring substituted at position 9 in a fluorene derivative represented by formula (8).
• the compound represented by formula (7) is the same as the compound represented by formula (7) described for Production method [I], and its details, amount of use and method of obtainment may be as described for the compound represented by formula (7) for Production method [I].
• step (a) will usually be carried out in the presence of an acid catalyst.
• the acid catalyst may be the same one used in step 2 of Production method [I], and the same description applies.
• step (a) The method for carrying out the reaction of step (a) is the same, other than changing the compound of formula (6) used in step 2 of Production method [I] to a compound of formula (3), and the same description applies.
• reaction mixture may be directly used as starting material for the following step (b), without isolation or purification.
• the compound represented by formula (8) may be precipitated from the obtained reaction mixture, and the compound represented by formula (8) may be precipitated at lower than 50°C after post-treatment such as rinsing, concentration, dilution and activated carbon treatment.
• the procedure for precipitating the compound represented by formula (8) from the reaction mixture that has been post-treated as necessary is carried out by raising the temperature of the reaction mixture, combined with a solvent if necessary, to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooling it to lower than 50°C.
• the reaction mixture When crystals of the compound represented by formula (1) precipitate from the reaction mixture at 50°C or higher, the reaction mixture may be mixed with a diluting solvent in an amount so that crystals do not precipitate out at 50°C or higher, and the temperature of the obtained mixture may then be raised to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooled to lower than 50°C.
• a diluting solvent in an amount so that crystals do not precipitate out at 50°C or higher
• the temperature of the obtained mixture may then be raised to 50°C or higher and no higher than the boiling point of the solvent (preferably 70 to 110°C), and then cooled to lower than 50°C.
• the diluting solvent may be any of the examples mentioned above as solvents to be used for the reaction, or an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol or pentanol or a carbonate solvent such as dimethyl carbonate or diethyl carbonate, but it is preferably ethanol or dimethyl carbonate, and most preferably ethanol.
• an alcohol solvent such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, isobutanol or pentanol
• a carbonate solvent such as dimethyl carbonate or diethyl carbonate, but it is preferably ethanol or dimethyl carbonate, and most preferably ethanol.
• the crystallization procedure may be carried out once or repeated several times.
• the acid catalyst in the reaction of step 2 is phosphotungstic acid
• using an alcohol such as ethanol allows a compound represented by formula (8) with a low palladium content to be obtained in a convenient and efficient manner with only a single crystallization procedure.
• the precipitated crystals are recovered by filtration, for example.
• the crystals may be rinsed using the solvent used for the reaction, and they may also be dried.
• the purity of the purified compound represented by formula (8) that is obtained in this manner is preferably 95% or greater.
• Ring Y in the compound represented by formula (4) or (5) is the same as ring Y in the compound represented by formula (4) or (5) in Production method [I], and the same description applies.
• step (b) the usage ratio of the compound represented by formula (4) with respect to 1 mol of the fluorene compound represented by formula (8) is the same as the usage ratio of the compound represented by formula (4) with respect to the fluorenone compound represented by formula (3) in step 1 of Production method [I], and the same description applies.
• step (b) the usage ratio of the compound represented by formula (5) with respect to 1 mol of the fluorene compound represented by formula (8) is the same as the usage ratio of the compound represented by formula (5) with respect to the fluorenone compound represented by formula (3) in step 1 of Production method [I], and the same description applies.
• reaction (dehalogenation reaction) between the compounds represented by formula (8) and formula (4) and/or (5) in step (b) may be carried out in a reaction solvent, in the presence of a base and a catalyst.
• the base used in the reaction of step (b) and the amount used is the same as the base used in the reaction of step 1 of Production method [I] and the amount used, and the same description applies.
• the palladium-based catalyst used in the reaction of step (b) is the same as the palladium-based catalyst used in the reaction of step 1 of the Production method [I], and the same description applies.
• step (b) the amount of catalyst used with respect to 1 mol of the fluorene compound represented by formula (8) is the same as the amount of catalyst used with respect to the fluorenone compound represented by formula (3) in step 1 of Production method [I], and the same description applies.
• reaction solvent used in step (b) and the amount used is the same as the reaction solvent used in step 1 of Production method [I] and the amount used, and the same description applies.
• the reaction temperature in step (b) may be the same as the reaction temperature in step 1 of Production method [I], and the same description applies.
• reaction mixture Upon completion of the reaction, the reaction mixture will generally contain unreacted fluorene, unreacted boronic acid, base, catalyst and secondary reaction products, in addition to the product compound represented by formula (1). These may be separated in the same manner as step 1 of Production method [I], and the same description applies.
• the purity of a compound with a fluorene backbone obtained by the production method of the invention may be selected within a wide range of 60 to 100%, but it is preferably 70% or greater, more preferably 80% or greater and even more preferably 90% or greater.
• the compounds with a fluorene backbone in the mixture of the invention preferably have a diphenylfluorene backbone or dinaphthylfluorene backbone in combination with an arene ring, they not only exhibit a high refractive index and high heat resistance, but can also reduce birefringence when used as polymers.
• fluorene compounds having aggregated arene rings substituted at position 9 of a fluorene backbone have been used, but this lowers the birefringence with the high refractive index and heat resistance.
• the compounds with a fluorene backbone in the mixture of the invention have low birefringence while still having a high refractive index, presumably because of the diphenylfluorene backbone.
• the arene ring has one or more hydroxyl groups and multiple hydroxyl groups in the fluorene compound as a whole, the reactivity is high.
• the mixture of the invention can be used as a starting material (monomer) for various types of resins.
• thermoplastic resin for example, a polyester resin, polycarbonate resin, polyester carbonate resin or polyurethane resin
• a polyol component for a thermosetting resin for example, an epoxy resin, phenol resin, thermosetting polyurethane resin or (meth)acrylate ((meth)acrylic acid ester.
• a compound with a fluorene backbone of the invention is to be used as a polyol component, a benzene ring is substituted at position 9 of the fluorene backbone and the fluorene backbone also has a diaryl group, which is presumably why the resulting resin provides the advantage of high levels for both high refractive index and low birefringence.
• the mixture of compounds with a fluorene backbone according to the invention can be used to efficiently prepare a derivative in a common solvent.
• the melting point of the compounds with a fluorene backbone in the mixture of the invention may be selected in a wide range of 100 to 300°C, preferably 120 to 280°C, more preferably 130 to 260°C, even more preferably 140 to 240°C and most preferably 150 to 210°C.
• the resins obtained in the Examples were measured using the following apparatus and method.
• the precipitated white crystals were removed by filtration and dried to obtain 140 g of white crystals of a partially purified product of 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene (70% yield, 95.2% purity).
• the partially purified product was again recrystallized with a toluene/butanol mixed solvent, to obtain 125 g of white crystals of a purified product of 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene (89% yield, 99.0% purity).
• Measurement of the residual metals by ICP showed Pd at 0.4 ppm.
• the pressure was reduced to 20 kPa over a period of 5 minutes while simultaneously increasing the temperature of the jacket to 260°C at a rate of 60°C/hr, for transesterification reaction.
• the jacket was kept at 260°C while reducing the pressure to 0.13 kPa over a period of 50 minutes, and polymerization reaction was carried out under conditions of 260°C, 0.13 kPa until a prescribed torque was reached.
• the produced resin was extracted while being pelletized, to obtain polycarbonate resin pellets.
• the obtained polycarbonate resin was analyzed by 1 H NMR, confirming that the 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene component had been introduced at 50 mol% with respect to the total monomer component.
• the refractive index of the obtained polycarbonate resin was 1.664, the Abbe number was 18, the Tg was 161°C and the pellet b* value was 8.0.
• Polycarbonate resin pellets were obtained in the same manner as Example 1, except that 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene synthesized by the method described above was used in step 3.
• the obtained polycarbonate resin was analyzed by 1 H NMR, confirming that the 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-diphenylfluorene component had been introduced at 50 mol% with respect to the total monomer component.
• the refractive index of the obtained polycarbonate resin was 1.664, the Abbe number was 18, the Tg was 161°C and the pellet b* value was 18.0.
• Synthesis of a fluorene compound was carried out in the same manner as Example 1, except that the amount of tetrakis(triphenylphosphine)palladium used in step 1 was changed to 0.558 g (0.48 millimole), but although the reaction proceeded, the diphenyl and monophenyl forms were mixed at 95:5 (weight ratio), and it was not possible to obtain the target fluorene compound.
• step (a) After cooling the reaction mixture observed in step (a) to room temperature, 58 mL of a 4 M potassium carbonate aqueous solution, 36.1 g (0.21 mol) of 2-naphthaleneboronic acid and 1.1 g (0.97 millimole) of tetrakis(triphenylphosphinepalladium) were added, and the mixture was stirred at 80°C for 2 hours for reaction. Progression of the reaction was confirmed by HPLC, and the reaction was completed upon confirming a BPDB residue amount of no greater than 0.1 wt%. The obtained reaction mixture was cooled to room temperature, and after adding ethanol to produce crystallization, the solid was filtered and collected.
• the collected solid was dissolved in chloroform and rinsed 3 times with hot water, after which the chloroform layer was subjected to decoloration treatment with active carbon and treated for palladium removal, and subsequently concentrated to obtain a partially purified product.
• the obtained partially purified solid product was recrystallized with toluene to obtain 58 g of white crystals of the target substance, 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene (80% yield, 98% purity).
• Measurement of the residual metals by ICP showed Pd at 2.0 ppm.
• step (b) After placing 25.91 parts by mass of the 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene synthesized in step (b), 16.44 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 16.23 parts by mass of diphenyl carbonate and 63.0 ⁇ 10 -5 parts by mass of sodium hydrogencarbonate in a reaction kiln equipped with a stirrer and distillation device, nitrogen exchange was carried out 3 times, and the jacket was heated to 200°C to melt the starting materials.
• the pressure was reduced to 20 kPa over a period of 5 minutes while simultaneously increasing the temperature of the jacket to 260°C at a rate of 60°C/hr, for transesterification reaction.
• the jacket was kept at 260°C while reducing the pressure to 0.13 kPa over a period of 50 minutes, and polymerization reaction was carried out under conditions of 260°C, 0.13 kPa until a prescribed torque was reached.
• the produced resin was extracted while being pelletized, to obtain polycarbonate resin pellets.
• the obtained polycarbonate resin was analyzed by 1 H NMR, confirming that the 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene component had been introduced at 50 mol% with respect to the total monomer component.
• the refractive index of the obtained polycarbonate resin was 1.692, the Abbe number was 15, and the Tg was 169°C.
• a white solid fluorene compound was obtained in the same manner as Example 9, except that the 2-naphthaleneboronic acid in step (b) was changed to 1-naphthaleneboronic acid (80% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 2.1 ppm.
• a white solid fluorene compound was obtained in the same manner as Example 9, except that the base in step (b) was changed to sodium carbonate (80% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 2.0 ppm.
• a white solid fluorene compound was obtained in the same manner as Example 9, except that the catalyst used was the acid catalyst of step (a) that had been dried under reduced pressure beforehand to remove the water of crystallization (81% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 2.2 ppm.
• a white solid fluorene compound was obtained in the same manner as Example 9, except that the acid catalyst in step (a) was changed to silicotungstic acid n-hydrate (H 4 [SiW 12 O 40 ] ⁇ nH 2 O) (79% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 2.5 ppm.
• a white solid fluorene compound was obtained in the same manner as Example 9, except that the catalyst used was the acid catalyst of step (a) that had been dried under reduced pressure beforehand to remove the water of crystallization (78% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 2.2 ppm.
• a brown solid fluorene compound was obtained in the same manner as Example 9, except that activated carbon treatment was not carried out in step (b) (79% yield, 97% purity). Measurement of the residual metals by ICP showed Pd at 50.1 ppm.
• Polycarbonate resin pellets were obtained in the same manner as Example 1, except that 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene synthesized by the method described above was used in step (c).
• the obtained polycarbonate resin was analyzed by 1 H NMR, confirming that the 9,9-bis(4-(2-hydroxyethoxy)phenyl)-2,7-dinaphthylfluorene component had been introduced at 50 mol% with respect to the total monomer component.
• the refractive index of the obtained polycarbonate resin was 1.692, the Abbe number was 15, and the Tg was 169°C.
• the color tone of the polycarbonate resin pellets obtained in Comparative Example 5 was a more intensely yellow color than the color tone of the polycarbonate resin pellets obtained in Example 9.
• a brown solid fluorene compound was obtained in the same manner as Example 9, except that the amount of tetrakis(triphenylphosphine)palladium used in step (b) was changed to 11.6 g (10 millimole) (80% yield, 98% purity). Measurement of the residual metals by ICP showed Pd at 120 ppm.
• Synthesis of a fluorene compound was carried out in the same manner as Example 9, except that the amount of tetrakis(triphenylphosphine)palladium used in step (b) was changed to 0.56 g (0.48 millimole), but although the reaction proceeded, the dinaphthyl and mononaphthyl forms were mixed at 90:10 (weight ratio) and it was not possible to obtain the target fluorene compound.
• the compounds with a fluorene backbone or their derivatives according to the invention, and resins using the novel compounds with a fluorene backbone as starting materials (monomers) can be used in optical members such as films, lenses, prisms, optical disks, transparent conductive panels, optical cards, sheets, optical fibers, optical films, optical filters and hard coat films, and in particular they are highly useful for lenses.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Polyesters Or Polycarbonates (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=67479306

Family Applications (1)

Country Status (7)

Cited By (3)

Families Citing this family (10)

Family Cites Families (13)

• 2019
  • 2019-01-29 JP JP2019569142A patent/JP7012751B2/ja active Active
  • 2019-01-29 CN CN201980006251.1A patent/CN111465589B/zh active Active
  • 2019-01-29 US US16/965,474 patent/US11339249B2/en active Active
  • 2019-01-29 WO PCT/JP2019/003024 patent/WO2019151264A1/fr unknown
  • 2019-01-29 EP EP19748185.6A patent/EP3747856A4/fr active Pending
  • 2019-01-29 KR KR1020207010829A patent/KR20200051797A/ko active IP Right Grant
  • 2019-01-30 TW TW108103502A patent/TW201940459A/zh unknown

Also Published As

Similar Documents

Legal Events